Indoles as insecticides and acaricides

ABSTRACT

There are provided methods for the control of insects and the protection of crops from the damage caused thereby which comprise the use of compositions comprising an indole compound of formula I   &lt;IMAGE&gt;

BACKGROUND OF THE INVENTION

Significant global economic losses in major agronomic crop productionare caused by the damage and infestation of insect and acarid pests.Such pest infestation can result in lower crop yields, lower cropquality, reduced consumption, increased perishability, increased risk ofdisease, higher processing cost, higher transportation cost andincreased market prices. Crop reduction due to said insect and acaridpests, for example in cotton and peanuts, ranges as high as 39% and 78%,respectively. Therefore, new and effective insect and acarid controlagents and crop protection methods are a continuing global need.

Therefore, it is an object of this invention to provide an effectivemethod for the control of pestiferous insects and acarina.

It is another object of this invention to provide a method for theprotection of growing and harvested crops from the harmful anddeleterious effects caused by insect and acarid attack and infestation.

It is a further object of this invention to provide insecticidal andacaricidal compounds and compositions and methods for their preparation.

SUMMARY OF THE INVENTION

The present invention provides a method for the control of insect andacarid pests which comprises contacting said pests or their food supply,habitat or breeding grounds with a pesticidally effective amount of acompound of formula I ##STR2## wherein R, Y and Z include electronwithdrawing groups and exclude electron donating groups, A is any groupcapable of enzymatic or hydrolytic cleavage and m is an integer of 1, 2,3 or 4.

The present invention also provides a method for the protection ofgrowing crops from the attack or infestation by insect or acarid pestswhich comprises applying to the foliage of the plants, or to the soil,water, or other medium in which they are growing, a pesticidallyeffective amount of a substituted indole compound of formula I.

This invention further describes compounds, compositions comprisingthose compounds, and methods for preparing those compounds, which areuseful as insecticidal and acaricidal agents.

DETAILED DESCRIPTION OF THE INVENTION

A wide variety of insects and acarina cause great economic loss bydamaging or destroying agricultural crops and horticultural andpharmaceutical plants; by aiding in the spread and development ofbacteria, fungi and viruses that produce diseases of plants; and bydestroying or devaluing stored foods, or other plant products andpossessions. Insect and acarid attack and infestation cause some of thefarmers' greatest problems the world over. The need for alternative andeffective insect and acarid control is a continuing global concern.

It has now been found that the substituted indole compounds of formula Iare highly effective agents for the control of a wide variety of insectand acarid pests.

The formula I indole compounds of the present invention include thosewhich have the structural formula ##STR3## wherein R, Y and Z includeelectron withdrawing groups and exclude electron donating groups, A isany group capable of enzymatic or hydrolytic cleavage and m is aninteger of 1, 2, 3 or 4.

In particular, the indole compounds of the present invention includethose formula I compounds wherein Y and Z are each independentlyhydrogen, halogen, CN, NO₂, S(O)_(n) R₁, C₁ -C₆ haloalkyl, C₁ -C₆haloalkoxy, COR₂, CSR₃, or W, with the proviso that only one of Y or Zmay be W, and with the further proviso that only one of Y or Z may behydrogen;

W is ##STR4## R is any combination of from one to four halogen, CN, NO₂,S(O)_(n) R₇, C₁ -C₆ haloalkyl or C₁ -C₆ haloalkoxy;

m is an integer of 1, 2, 3 or 4;

n is an integer of 0, 1, or 2;

L, M and Q are each independently hydrogen, halogen NO₂ , CN, C₁ -C₄haloalkyl, C₁ -C₄ haloalkoxy, COR₇ or S(O)_(n) R₈ ;

R₁, R₂, R₃, R₇ and R₈ are each independently C₁ -C₆ haloalkyl;

X is O or S;

R₄, R₅ and R₆ are each independently hydrogen, halogen, NO₂, CN,S(O)_(n) R₉ or R₅ and R₆ may be taken together with the atoms to whichthey are attached to form a ring in which R₅ R₆ is represented by thestructure ##STR5## R₁₀, R₁₁, R₁₂ and R₁₃ are each independentlyhydrogen, halogen, CN, NO₂ or S(O)_(n) R₁₄ ;

R₉ and R₁₄ are each independently C₁ -C₆ haloalkyl;

A is R₁₅, OR₁₅ or CN;

R₁₅ is hydrogen, COR₁₆, CHR₁₇ NHCOR₁₈, CH₂ SQ₁, ##STR6## C₁ -C₆ alkyloptionally substituted with one to three halogen atoms,

one tri(C₁ -C₄ alkyl)silyl,

one hydroxy,

one cyano,

one or two C₁ -C₄ alkoxy groups optionally substituted with one to threehalogen atoms,

one C₁ -C₄ alkylthio,

one phenyl optionally substituted with one to three halogen atoms, oneto three C₁ -C₄ alkyl groups or one to three C₁ -C₄ alkoxy groups,

one phenoxy group optionally substituted with one to three halogenatoms, one to three C₁ -C₄ alkyl groups or one to three C₁ -C₄ alkoxygroups,

one benzyloxy group optionally substituted on the phenyl ring with oneto three halogen atoms, one to three C₁ -C₄ alkyl groups or one to threeC₁ -C₄ alkoxy groups,

one C₁ -C₆ alkylcarbonyloxy group optionally substituted with one tothree halogen atoms,

one C₂ -C₆ alkenylcarbonyloxy group optionally substituted with one tothree halogen atoms,

one phenylcarbonyloxy group optionally substituted with one to threehalogen atoms, one to three C₁ -C₄ alkyl groups or one to three C₁ -C₄alkoxy groups,

one C₁ -C₆ alkoxycarbonyl group optionally substituted with one to threehalogen atoms or one to three C₁ -C₄ alkoxy groups, or

one benzylcarbonyloxy group optionally substituted on the phenyl ringwith one to three halogen atoms, one to three C₁ -C₄ alkyl groups or oneto three C₁ -C₄ alkoxy groups,

C₃ -C₆ alkenyl optionally substituted with one to three halogen atoms orone phenyl group or

C₃ -C₆ alkynyl optionally substituted with one to three halogen atoms orone phenyl group;

R₁₆ is C₁ -C₆ alkyl or C₃ -C₆ cycloalkyl each optionally substitutedwith one to three halogen atoms,

one hydroxy,

one cyano,

one or two C₁ -C₄ alkoxy groups optionally substituted with one to threehalogen atoms,

one C₁ -C₄ alkylthio,

one phenyl group optionally substituted with one to three halogen atoms,one to three C₁ -C₄ alkyl groups or one to three C₁ -C₄ alkoxy groups,

one phenoxy group optionally substituted with one to three atoms, one tothree C₁ -C₄ alkyl groups or one to three C₁ -C₄ alkoxy groups,

one benzyloxy group optionally substituted on the phenyl ring with oneto three C₁ -C₄ alkyl groups or one to three halogen atoms, one to threeC₁ -C₄ alkoxy groups,

one C₁ -C₆ alkylcarbonyloxy group optionally substituted with one tothree halogen atoms,

one C₂ -C₆ alkenylcarbonyloxy group optionally substituted with one tothree halogen atoms,

one phenylcarbonyloxy group optionally substituted with one to threehalogen atoms, one to three C₁ -C₄ alkyl groups or one to three C₁ -C₄alkoxy groups,

one C₁ -C₆ alkoxycarbonyl group optionally substituted with one to threehalogen atoms or one to three C₁ -C₄ alkoxy groups, or

one benzylcarbonyl group optionally substituted on the phenyl ring withone to three halogen atoms, one to three C₁ -C₄ alkyl groups or one tothree C₁ -C₄ alkoxy groups,

C₂ -C₆ alkenyl optionally substituted with one to three halogen atoms orone phenyl group,

C₃ -C₆ alkynyl optionally substituted with one to three halogen atoms orone phenyl group,

phenyl optionally substituted with one or more halogen, C₁ -C₄ alkyl, C₁-C₄ alkoxy, phenoxy, C₁ -C₄ alkylthio, tri(C₁ -C₄ alkyl)silyl, C₁ -C₄alkylsulfinyl, C₁ -C₄ alkylsulfonyl, CN, NO₂ or CF₃ groups,

phenoxy optionally substituted with one or more halogen, C₁ -C₄ alkyl,C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, tri(C₁ -C₄ alkyl)silyl, C₁ -C₄alkylsulfinyl, C₁ -C₄ alkylsulfonyl, CN, NO₂ or CF₃ groups,

1- or 2-naphthyl,

2-, 3-, or 4-pyridyl optionally substituted with halogen,

C₁ -C₆ alkoxy optionally substituted with halogen, or

C₂ -C₆ alkenyloxy optionally substituted with halogen;

R₁₇ is hydrogen or C₁ -C₄ alkyl;

R₁₈ is C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₁ -C₆ alkoxy, C₁ -C₆ haloalkoxy,

phenyl optionally substituted with halogen, CN, NO₂, C₁ -C₄ alkyl, C₁-C₄ alkoxy or CF₃,

2- or 3-thienyl, or

2 - or 3- furyl;

Q₁ is ##STR7## CN, C₁ -C₆ alkyl optionally substituted with halogen, CNor phenyl group, or

phenyl optionally substituted with one or more halogen, C₁ -C₄ alkyl, C₁-C₄ alkoxy, CN, NO₂, CF₃ or NR₃₃ R₃₄ ;

A₁ is O or S;

R₂₂ is C₁ -C₆ alkyl or phenyl;

R₂₃ is C₁ -C₆ alkyl;

R₂₄ and R₂₅ are each independently hydrogen, C₁ -C₆ alkyl or may betaken together with the atom to which they are attached to form a 5- to7-membered ring;

R₂₆ is C₁ -C₄ alkyl;

R₂₇ is hydrogen, C₁ -C₄ alkyl or may be taken together with either R₂₈or R₂₉ and the atoms to which they are attached to form a 5- to7-membered ring optionally substituted with one or two C₁ -C₄ alkylgroups;

R₂₈ and R₂₉ are each independently hydrogen or C₁ -C₄ alkyl;

R₃₀ is C₁ -C₄ alkyl or when taken together with R₂₇ and the atoms towhich they are attached may form a 5- to 7-membered ring optionallysubstituted with one or two C₁ -C₄ alkyl groups;

R₃₁ and R₃₂ are each independently hydrogen, C₁ -C₄ alkyl or when takentogether may form a ring wherein R₃₁ R₃₂ is represented by--CH═CH--CH═CH--;

R₃₃ and R₃₄ are each independently hydrogen or C₁ -C₄ alkyl;

R₁₉ is hydrogen or C₁ -C₄ alkyl;

R₂₀ and R₂₁ are each independently hydrogen,

C₁ -C₆ alkyl optionally substituted with halogen,

C₁ -C₆ alkoxy optionally substituted with halogen,

C₁ -C₆ alkylthio optionally substituted with halogen, or

phenyl optionally substituted with halogen, NO₂, CN, C₁ -C₄ alkyloptionally substituted halogen, or C₁ -C₄ alkoxy optionally substitutedwith halogen, or

when R₂₀ and R₂₁ are taken together with the atom to which they areattached may form a C₃ -C₆ cycloalkyl group optionally substituted withC₁ -C₄ alkyl, C₂ -C₆ alkenyl or phenyl, or R₂₀ or R₂₁ may be takentogether with R₃₅ and the atoms to which they are attached to form a 4-to 7-membered heterocyclic ring;

x is an integer of 0, 1, 2, 3 or 4;

Q₂ is A₂ R₃₅, ##STR8## NR₃₇ R₃₈, CR₃₉ R₄₀, COR₄₁, or C₃ -C₆ cycloalkyloptionally substituted with one or more C₁ -C₆ alkyl, C₂ -C₆ alkenyl, or

phenyl optionally substituted with halogen, NO₂, CN, C₁ -C₄ alkyl, C₁-C₄ haloalkyl, C₁ -C₄ alkoxy, or C₁ -C₄ haloalkoxy;

A₂ is O or S(O)p;

p is an integer of 0, 1 or 2;

R₃₅ is hydrogen, C₁ -C₆ alkyl, C₂ -C₆ alkenyl, C₂ -C₆ alkynyl, phenyloptionally substituted with halogen,

NO₂, CN,

C₁ -C₄ alkyl optionally substituted with halogen,

C₁ -C₄ alkoxy optionally substituted with halogen,

COR₄₂ provided p is O,

COR₄₃ provided p is O,

(CH₂ CH₂ O)_(q) R₄₄, or ##STR9## R₃₅ may be taken together with eitherR₂₀ or R₂₁ and the atoms to which they are attached to form a 4- to7-membered heterocyclic ring;

A₃ is O or S;

R₄₂ and R₄₄ are each independently C₁ -C₆ alkyl, C₂ -C₆ alkenyl, C₂ -C₆alkynyl, or

phenyl optionally substituted with halogen, NO₂, CN, C₁ -C₄ alkyloptionally substituted with halogen, or

C₁ -C₄ alkoxy optionally substituted with halogen;

q is an integer of 1, 2 or 3;

R₄₃ is OR₄₇ or NR₄₈ R₄₉ ;

R₄₇ is C₁ -C₆ alkyl or

phenyl optionally substituted with halogen, NO₂, CN,

C₁ -C₄ alkyl optionally substituted with halogen, or

C₁ -C₄ alkoxy optionally substituted with halogen;

R₄₈ and R₄₉ are each independently hydrogen or C₁ -C₄ alkyl;

R₄₅ and R₄₆ are each independently hydrogen or C₁ -C₄ alkyl, or whentaken together may form a ring wherein R₄₅ R₄₆ is represented by--CH═CH--CH═CH--;

R₃₆ is C₁ -C₄ alkyl;

R₃₇ is hydrogen, C₁ -C₆ alkyl, C₂ -C₆ alkenyl, C₂ -C₆ alkynyl, or

phenyl optionally substituted with halogen, NO₂, CN,

C₁ -C₄ alkyl optionally substituted with halogen, or

C₁ -C₄ alkoxy optionally substituted with halogen, or

R₃₇ may be taken together with either R₂₀ or R₂₁ and the atoms to whichthey are attached to form a 4- to 7-membered heterocyclic ring;

R₃₈ is hydrogen, C₁ -C₆ alkyl, C₂ -C₆ alkenyl, C₂ -C₆ alkynyl,

phenyl optionally substituted with halogen, NO₂, CN,

C₁ -C₄ alkyl optionally substituted with halogen, or

C₁ -C₄ alkoxy optionally substituted with halogen, ##STR10## CN, SO₂ R₅₁or COCHR₅₂ NHR₅₃ ; A₄ is O or S;

R₅₀ is OR₅₄, CO₂ R₅₅, NR₅₆ R₅₇,

C₁ -C₆ alkyl optionally substituted with halogen,

C₂ -C₆ alkenyl, C₂ -C₆ alkynyl or

phenyl optionally substituted with halogen, NO₂, CN,

C₁ -C₄ alkyl optionally substituted with halogen, or

C₁ -C₄ alkoxy optionally substituted with halogen;

R₅₄ and R₅₅ are each independently C₁ -C₆ alkyl optionally substitutedwith one phenyl group, or

phenyl optionally substituted with halogen, NO₂, CN,

C₁ -C₄ alkyl optionally substituted with halogen, or

C₁ -C₄ alkoxy optionally substituted with halogen;

R₅₆ and R₅₇ are each independently hydrogen or C₁ -C₄ alkyl;

R₅₁ is NR₅₈ R₅₉, C₁ -C₆ alkyl, C₂ -C₆ alkenyl, C₂ -C₆ alkynyl, or

phenyl optionally substituted with halogen, NO₂, CN,

C₁ -C₄ alkyl optionally substituted with halogen, or

C₁ -C₄ alkoxy optionally substituted with halogen;

R₅₈ and R₅₉ are each independently hydrogen or C₁ -C₄ alkyl;

R₅₂ is hydrogen, C₁ -C₄ alkyl optionally substituted with

hydroxy, SR₆₀, CONH₂, NH₂,

NHC(═NH) NH₂, CO₂ H,

phenyl optionally substituted with hydroxy,

3-indolyl or

4-imidazolyl;

R₆₀ is hydrogen or C₁ -C₄ alkyl;

R₅₃ is ##STR11## R₆₁ is C₁ -C₆ alkyl optionally substituted withhalogen, C₁ -C₆ alkoxyalkyl, C₁ -C₆ alkylthio,

phenyl optionally substituted with halogen, NO₂, CN,

C₁ -C₄ alkyl optionally substituted with halogen, or

C₁ -C₄ alkoxy optionally substituted with halogen,

OR₅₄, CO₂ R₅₅ or NR₅₆ R₅₇ ;

R₃₉ and R₄₀ are each independently hydrogen,

C₁ -C₆ alkyl optionally substituted with halogen,

C₁ -C₆ alkoxy optionally substituted with halogen,

C₁ -C₆ alkylthio optionally substituted with halogen,

phenyl optionally substituted with halogen, CN, NO₂,

C₁ -C₄ alkyl optionally substituted with halogen, or

C₁ -C₄ alkoxy optionally substituted with halogen, or

when R₃₉ and R₄₀ are taken together with the atom to which they areattached may form a C₃ -C₆ cycloalkyl ring optionally substituted withC₁ -C₄ alkyl, C₂ -C₆ alkenyl or phenyl;

R₄₁ is OR₆₂, NR₅₈ R₅₉, C₁ -C₄ alkyl or

phenyl optionally substituted with halogen, CN, NO₂,

C₁ -C₄ alkyl optionally substituted with halogen, or

C₁ -C₄ alkoxy optionally substituted with halogen;

R₆₂ is C₁ -C₄ alkyl or

phenyl optionally substituted with halogen, CN, NO₂,

C₁ -C₄ alkyl optionally substituted with halogen, or

C₁ -C₄ alkoxy optionally substituted with halogen.

The term halogen as used in the specification and claims designateschlorine, fluorine, bromine or iodine. The term haloalkyl designates analkyl group, C_(n) H_(2n+1) which contains from one halogen atom to 2n+1halogen atoms wherein the halogen atoms may be the same or different.

It is contemplated, that A may be any group that is capable of enzymaticor hydrolytic cleavage and Y, Z and R may be any combination of from 2to 6 electron withdrawing groups that are also lipophilic. Suitableelectron withdrawing groups include halogen, nitro, cyano,trifluoromethylsulfonyl, trifluoroacetyl, and the like.

Preferred compounds of the invention are those compounds of formula Iwherein Y and Z are each independently hydrogen, halogen, CN, NO₂,S(O)_(n) R₁, C₁ -C₆ haloalkyl or C₁ -C₆ haloalkoxy provided only one ofY or Z is hydrogen; m is 3 or 4 and n is 1 or 2.

Also preferred are those compounds wherein Y is hydrogen, CN, NO₂,S(O)_(n) R₁, C₁ -C₆ haloalkyl or C₁ -C₆ haloalkoxy or C₁ -C₆ haloalkyland Z is phenyl optionally substituted with L, M, Q.

More preferred compounds are those compounds of formula I wherein Y isCN, C₁ -C₆ haloalkyl or SO₂ R₁ and Z is C₁ -C₆ haloalkyl, SO₂ R₁, orphenyl optionally substituted with L, M, Q.

Compounds of formula I wherein Y or Z is C₁ -C₆ haloalkyl may beprepared by literature procedures such as that described by Y. Kobayashiet al in the Journal of Organic Chemistry 39, 1836 (1974) or by thereaction of the appropriate haloprecursor of formula II (wherein thehalogen is I) with a C₁ -C₆ haloalkylcarboxylate salt or ester andcopper (I) halide as shown in flow diagram I wherein the C₁ -C₆haloalkylcarboxylate is sodium trifluoroacetate. ##STR12##

Compounds of formula I wherein Y or Z are CN may be prepared by reactingthe above-prepared haloalkyl intermediate with chlorosulfonylisocyanate(CSI) in the presence of acetonitrile and dimethylformamide (DMF) asshown in flow diagram II. ##STR13##

Compounds of formula I wherein Z is S(O)_(n) R₁ may be prepared from theappropriate indolenethione precursor of formula III by reaction with asuitable halogenated alkene such as chlorotrifluoroethylene in thepresence of a base to give the formula I products wherein n is 0. Thishaloalkylthio compound may then be oxidized in the usual manner to yieldthe sulfone and sulfoxide analogs as shown in diagram III. ##STR14##

Alternatively, compounds of formula I wherein Y or Z is S(O)_(n) R₁, maybe prepared by reacting the appropriate indole precursor withhaloalkylsulfenyl chloride and, if desired, oxidizing the haloalkylthioindole as shown above. The reaction sequence is shown in flow diagramIV. ##STR15##

Compounds of formula I wherein Z is W may be prepared by the cyclizationof the appropriate aryl hydrazone of phenyl (or substituted phenyl)hydrazine with polyphosphoric acid (PPA). For example, when W is phenyl,the hydrazone of formula IV is cyclized as shown in flow diagram V.##STR16##

Formula I compounds wherein A is other than hydrogen may be prepared byreacting the NH indole precursor with the appropriate alkyl or carbonylhalide in the presence of a base to give products of formula I as shownin flow diagram VI. ##STR17##

The formula I products wherein Y or Z or R are halogen or NO₂ may beobtained by standard halogenation or nitration procedures known in theart. These and other methods for the preparation of substituted indolederivatives of formula I will become apparent from the examples setforth below.

Substituted formula I indoles and the N-substituted derivatives thereofare effective for the control of insect and acarid pests and for theprotection of growing and harvested plants and crops from attack andinfestation by said pests.

In practice, generally about 10 ppm to 10,000 ppm, preferably about 100to 5,000 ppm of the formula I compound dispersed in an agronomicallyacceptable liquid carrier, when applied to the plants or the soil,water, or other medium in which they are growing, is effective toprotect the plants from insect and acarina attack and infestation.Applications, such as spray applications, of compositions of theinvention are generally effective at rates which provide about 0.125kg/ha to about 250 kg/ha, preferably about 1 kg/ha to 200 kg/ha, mostpreferably about 10 kg/ha to 100 kg/ha of active ingredient. Of course,it is contemplated that higher or lower rates of application of thesubstituted indole derivatives may be used depending upon the prevailingenvironmental circumstances such as population density, degree ofinfestation, stage of plant growth, soil conditions, weather conditionsand the like.

Advantageously, the formula I compounds may be used in conjunction with,or in combination with, other biological and chemical control agentsincluding other insecticides, nematicides, acaricides, molluscides,fungicides and bactericides such as nuclear polyhedrosis viruses,pyrroles, arylpyrroles, halobenzoylureas, pyrethroids, carbamates,phosphates, and the like.

Typical formulations suitable for the formula I indole derivatives aregranular compositions, flowable compositions, wettable powders, dusts,microemulsions, emulsifiable concentrates and the like. All compositionswhich lend themselves to soil, water and foliage application and provideeffective plant protection are suitable. Compositions of the inventioninclude the formula I substituted indole derivative admixed with anagronomically acceptable inert solid or liquid carrier.

Where compositions of the invention are to be employed in combinationtreatments with other biological or chemical agents, the composition maybe applied as an admixture of the components or may be appliedsequentially. While not required, the combination composition comprisinga formula I compound and a co-pesticide may also comprise othercomponents, for example, fertilizers, inert formulation aides such assurfactants, emulsifiers, wetting agents, defoamers, dyes, extenders andthe like.

For a more clear understanding of the invention, specific examplesthereof are set forth below. The invention described and claimed hereinis not to be limited in scope by these merely illustrative examples.Indeed, various modifications of the invention in addition to thoseexemplified and described herein will become apparent to those skilledin the art from the following examples and the foregoing description.Such modifications are also intended to fall with in the scope of theappended claims. The terms ¹ H, ¹³ C, ¹⁹ FNMR designate proton, carbonand fluorine nuclear magnetic resonance (NMR) spectroscopy,respectively. IR designates infrared spectroscopy, and GC and TLCdesignate gas chromatography and thin layer chromatography,respectively.

EXAMPLE 1

Preparation of 2-(Trifluoromethyl)indole ##STR18##

A 2.5M solution of n-butyl lithium in hexanes (8.8 mL, 22 mmole) at roomtemperature, under N₂, is treated withN,N,N',N'-tetramethylethylenediamine (TMEDA) (3.3 mL, 22 mole), stirredat room temperature for 0.5 hour, treated withN-trimethylsilyl-o-toluidine (1.79 g, 10 mmole), heated at refluxtemperature for 6 hours, cooled to -78° C., treated with ethyltrifluoroacetate (1.4 mL, 12 mmole) stirred at -78° C. for 0.25 hour,warmed to room temperature, diluted with water and extracted withdiethyl ether. The combined extracts are washed sequentially with 1N HCland saturated NaHCO₃, dried over MgSO₄ and concentrated in vacuo to givea residue. The residue is chromatographed using silica gel and 4:1hexanes:ethyl acetate as eluent to afford the title product as a lightyellow solid, mp 104°-106° C. (literature mp 102° C.¹), 0.81 g (47%yield), further identified by IR, .sup. 1 HNMR and ¹⁹ FNMR analyses.

¹ Y. Kobayashi, I. Kumadaki, Y. Hirose and

Y. Hanazawa, Journal of Organic Chemistry, 39, 1836 (1974).

EXAMPLE 2

Preparation of N-Methyl-2-(trifluoromethyl)indole ##STR19##

A mixture of 1-methyl-2-iodoindole (4.40 g, 17.3 mmole), sodiumtrifluoroacetate (24.0 g, 176.5 mmole) and copper(I)iodide (17.1 g, 89.8mmole)in N-methylpyrrolidone is heated at 160° C. for 6 hours, cooled toroom temperature, diluted with water and filtered through diatomaceousearth to remove copper salts. The filtrate is extracted with ether. Theextracts are combined, washed with water, dried over MgSO₄ andconcentrated in vacuo to give a residue. The residue is chromatographedusing silica gel and 4:1 hexanes:ethyl acetate as eluent to give thetitle product as a pale yellow oil which crystallized on standing, 119 g(37% yield), mp 28°-32° C., identified by IR, ¹ HNMR and ¹⁹ FNMRanalyses.

EXAMPLE 3

Preparation of 5-Chloro-2-iodo-1-methylindole ##STR20##

A mixture of 5-chloro-1-methylindole (10.0 g, 60.4 mmole) and n-butyllithium (29 mL of 2.5M sol'n in hexanes, 72.5 mmole) in diethyl ether isheated at reflux temperature for 3 hours, cooled to 0° C., treated withiodine (18.4 g, 72.5 mmole), stirred at 0° C. for 1 hour, warmed to roomtemperature, stirred for 1 hour, and treated with aqueous sodiumsulfite. After phase separation, the organic phase is dried over MgSO₄and concentrated in vacuo to give the title product as a brown oil whichsolidified on standing, 16.5 g (93.7% yield). The title product is usedas in Example 4.

EXAMPLE 4

Preparation of 5-Chloro-1methyl-2-(trifluoromethyl)indole ##STR21##

A mixture of 5-chloro-2-iodo-1-methylindole obtained from Example 3(16.5 g, 56.6 mmole), sodium trifluoroacetate (76.2 g, 56.0 mmole) andcopper (I) iodide (10.6 g, 56.0 mmole) in N-methylpyrrolidone is heatedat 160° C. for about 8 hours, cooled to room temperature, diluted withwater and filtered through diatomaceous earth. The filtrate is extractedwith diethyl ether. The extracts are combined, washed with water, driedover MgSO₄ and concentrated in vacuo to give a black oil residue. Theresidue is chromatographed using silica gel and 15:1 hexanes:ethylacetate to give a yellow oil. The oil is chromatographed a second timeusing the same eluent and silica gel to give the title product as ayellow oil, 2.92 g (22% overall yield from 5-chloro-1-methylindole),identified by IR, ¹ HNMR, ¹³ CNMR and ¹⁹ FNMR analyses.

EXAMPLE 5

Preparation of 5-Chloro-3-cyano-1-methyl-2-(trifluoromethyl)indole##STR22##

A solution of 5-chloro-1-methyl-2-(trifluoromethyl)indole (1.79 g, 7.7mmole) in acetonitrile is cooled to 0° C., treated withchlorosulfonylisocyanate (CSI) (1.0 mL 11.5 mmole) stirred untilstarting indole cannot be observed by thin layer chromatography, treatedwith 5 mL of dimethylformamide (DMF), stirred for 0.5 hour and dilutedwith diethyl ether and water. The phases are separated. The organicphase is washed with water, dried over Na₂ SO₄ and concentrated invacuo. The resultant residue is chromatographed using silica gel and 4:1hexanes:ethyl acetate as eluent to give the title product as a whitesolid, 0.99 g (49.7% yield) mp 166°-167.5° C., identified by IR, ¹ HNMR,¹³ CNMR, ¹⁹ FNMR and mass spectral analyses.

EXAMPLE 6

Preparation of 6-Chloroindole ##STR23##

A mixture of 4-chloro-2-nitrotoluene (34 g, 0.2 mole), dimethylformamidedimethyl acetal (28 mL, 0.2 mole) and pyrrolidine (25 mL 0.3 mole) indimethylformamide (DMF) is heated at 100° C. for 72 h, cooled to roomtemperature and concentrated in vacuo to give a deep red residue. Theresidue is taken up in methanol/tetrahydro-furan (1:1), treated withabout 2 mL of a Raney nickel slurry and hydrogenated at atmosphericpressure. The reaction is monitored by GC, TLC and H₂ uptake. After 2hours, the hydrogenation is continued at 20 psi-40 psi for a totalhydrogenation time of 24 hours. The resultant reaction mixture isfiltered through diatomaceous earth. The filtercake is washed withmethylene chloride and the combined filtrate is washed sequentially with1N HCl and saturated NaHCO₃, dried over MgSO₄ and concentrated in vacuoto give a brown oil residue. The residue is crystallized in hexanes togive the title product as a brown solid, 22 g (72.6% yield), identifiedby IR, ¹ HNMR, ¹³ CNMR and mass spectral analyses.

EXAMPLE 7

Preparation of 6-Chloro-1-methylindole ##STR24##

A mixture of 6-chloroindole (22.0 g, 0.145 mole) and potassiumt-butoxide (KOt-Bu) (20.0 g 0.179 mole) in tetrahydrofuran at roomtemperature is treated dropwise with methyl iodide (11.2 mL, 0.179mole), allowed to stir at ambient temperatures for about 1 hour anddiluted with a mixture of pet ether and water. The phases are separated.The organic phase is washed with 1N HCL and water, dried over Na₂ SO₄and concentrated to a brown oil. After chromatography (silica gel/4:1hexanes:ethyl acetate), the oil is distilled to afford the title productas a colorless oil, 16.25 g (67% yield), bp 110°-115° C./4 mm Hg,identified by IR, ¹ HNMR, ¹³ CNMR, mass spectral and microanalyses.

EXAMPLE 8

Preparation of 6-Chloro-2-iodo-1-methylindole ##STR25##

A solution of 6-chloro-1-methylindole (0.83 g, 5.0 mmole) in diethylether is treated with 1.7M t-butyl lithium in hexanes (3.5 mL, 6.0mmole) at 0° C., stirred at ambient temperatures for 0.25 hour, treatedwith I₂ (1.52 g, 6.0 mmole), stirred at room temperature until reactionis complete by TLC analysis, treated with aqueous sodium sulfite andextracted with diethyl ether. The combined ether extracts are dried overMgSO₄ and concentrated in vacuo to afford the title product as a brownsolid, 1.52 g (contains ether). The product is used as is in Example 9.

EXAMPLE 9

Preparation of 6-Chloro-1-methyl-2-(trifluoromethyl)indole ##STR26##

A mixture of 6-chloro-2-iodo-1-methylindole, obtained in Example 8, (1.5g (96.7% purity), 5.0 mmole), sodium trifluoroacetate (6.8 g, 50 mmole)and copper (I) iodide (0.95 g, 5.0 mmole) in N-methylpyrrolidone isheated at about 160° for 2 hours and 190° C. for 1 hour, cooled to roomtemperature, diluted with water and filtered through diatomaceous earth.The filtrate is extracted with diethyl ether. The combined extracts arewashed with water, dried over MgSO₄ and concentrated in vacuo to give aresidue. The residue is chromatographed (silica gel/4:1 hexanes:ethylacetate) to afford the title product as a yellowish crystalline solid0.51 g (46% yield), mp 75°-78° C., identified by IR, ¹ HNMR, ¹³ CNMR, ¹⁹FNMR, mass spectral and microanalyses.

EXAMPLE 10

Preparation of6-Chloro-1-methyl-2-(trifluoromethyl)indole-3-carbonitrile ##STR27##

Using essentially the same procedure described in Example 5, the titleproduct is obtained as a white solid in 80.4% yield afterchromatography, mp 142.5°-145° C., identified by IR, ¹ HNMR, ¹³ CNMR, ¹⁹FNMR and mass spectral analyses.

EXAMPLE 11

Preparation of6-Chloro-1-(ethoxymethyl)-2-(trifluoromethyl)indole-3-carbonitrile##STR28##

A mixture of 6-chloro-3-cyano-1-methyl-2-(trifluoromethyl)indole (1.08g, 4.2 mmole) and thionyl chloride (0.68 mL, 8.4 mmole) in carbontetrachloride is heated at reflux temperature for 18 hours, cooled toroom temperature and concentrated in vacuo for 18 hours to remove allvolatiles. The residue is dissolved in ethanol and treated with asolution of sodium metal (0.38 g, 16 mmole) in ethanol, stirred or 0.5hour at room temperature and diluted with diethyl ether. The dilutedreaction mixture is washed with water, dried over Na₂ SO₄ andconcentrated in vacuo to give a residue. The residue is chromatographed(silica gel/4:1 hexanes: ethyl acetate) to afford the title product asan off-white solid, 0.66 g (52% yield) mp 83°-86° C., identified by IR,¹ HNMR, ¹³ CNMR, ¹⁹ FNMR and mass spectral analyses.

EXAMPLE 12

Preparation of 6-Chloro-3-nitro-1-methyl-2-(trifluoromethyl)indole##STR29##

A solution of 6-chloro-1-methyl-2-(trifluoromethyl)indole (1.16 g, 5.0mmole ) in acetic anhydride is treated with Cu(NO₃)₂.3H₂ O (1.20 g, 5.0mmole) stirred at 0°-25° C. for 3 hours, and partitioned between waterand diethyl ether. The organic phase is washed with water and saturatedNaHCO₃, dried over Na₂ SO₄ and concentrated in vacuo to give a residue.The residue is chromatographed (silica gel/4:1 hexanes: ethyl acetate)to afford the title product as white leaflets, 0.87 g (62.41% yield), mp157°-159.9° C., identified by IR, ¹ HNMR, ¹³ CNMR, ¹⁹ FNMR and massspectral analyses.

EXAMPLE 13

Preparation of 5-Bromo-2-(trifluoromethyl)indole-3-carbonitrile##STR30##

A solution of 3-cyano-2-(trifluoromethyl)indole (1.05 g, 5.0 mmole) inacetic acid is treated with Br₂ (0.6 mL, 6.0 mmole) at room temperature,and stirred until reaction is complete by TLC. The reaction mixture isworked up as described in Example 22 to afford the title product as awhite solid after chromatography (silica gel and 4:1 hexanes:ethylacetate) and crystallization, 0.95 g (65% yield), mp 188°-191.5° C.,identified by IR, ¹ HNMR, ¹⁹ FNMR and mass spectral analyses.

EXAMPLE 14

Preparation of 5,6- and6,7-Dichloro-3-cyano-1-methyl-2-(trifluoromethyl)indole ##STR31##

A suspension of 6-chloro-3-cyano-2-(trifluoromethyl)indole (0.51 g, 2.0mmole) in 2 mL H₂ SO₄ and 6 mL water is treated with acetic acid toachieve dissolution; the solution is treated with incremental portionsof NaOCl (2.8 mL, 2.0 mmole) and H₂ SO₄ until reaction is complete (atotal of 4 portions, 8.0 mmole NaOCl). The resultant reaction mixture ispoured into water and extracted with diethyl ether. The organic phase iswashed with NaHCO₃ until neutralized, dried over MgSO₄ and concentratedin vacuo to give a residue containing the title product mixture. Themixture is separated by column chromatography (silica gel/4:1 hexanes:ethyl acetate) to afford:

A--5,6 dichloro-3-cyano-1-methyl-2-(trifluoromethyl)indole as a whitesolid, 0.077 g (13% yield), mp 175°-180° C., identified by IR, ¹ HNMR,¹⁹ FNMR and mass spectral analyses, and

B--6,7-dichloro-3-cyano-1-methyl-2-(trifluoromethyl)indole as a whitesolid, 0.082 g (14% yield), mp 220°-223° C., identified by IR, ¹ HNMR,¹⁹ FNMR and mass spectral analyses.

EXAMPLE 15

Preparation of 5,6-Dichloro-2-(trifluoromethyl)indole and5,6-dichloro-1-ethoxy-2-(trifluoromethyl)indole ##STR32##

A mixture of 4,5-dichloro-2-nitro-β-trifluoromethyl styrene (5.5 g, 19.2mmole) and triethylphosphite (26 mL, 153 mmole) is heated at 160° C. for4.5 hours (monitored by GC, TLC and NMR), cooled to room temperature,concentrated in vacuo to give a residue. The residue is taken up inether, washed sequentially with water and brine, dried over MgSO₄ andconcentrated in vacuo to afford the title product mixture. The mixtureis separated chromatographically (silica gel/10:1 hexanes:ethyl acetate)to afford:

A--5,6 dichloro-2-(trifluoromethyl)indole as colorless leaflets 0.82 g(17% yield)mp 96°-98° C., identified by IR, ¹ HNMR, ¹³ CNMR, ¹⁹ FNMR andmass spectral analyses, and

B--5,6-dichloro-1-ethoxy-2-(trifluoromethyl)-indole as a yellow solid,1.19 g (20.7% yield, mp 71°-73.5° C., identified by IR, ¹ HNMR, ¹⁹ FNMRand mass spectral analyses.

EXAMPLE 16

Preparation of6,7-Dichloro-1-(ethoxymethyl)-2-(trifuloromethyl)indole-3-carbonitrile##STR33##

Using essentially the same procedure described in Example 11 the titleproduct is obtained in 44% yield after chromatography (silica gel/4:1hexanes:ethyl acetate) as a white solid, mp 122°-127° C., identified byIR, ¹ HNMR, ¹⁹ FNMR and mass spectral analyses.

EXAMPLE 17

Preparation of 5,6-Dichloro-2-(trifluoromethyl)indole-3-carbonitrile##STR34##

Using essentially the same procedure described in Example 5, the titleproduct is obtained in 19.6% yield after chromatography (silica gel/8:1hexanes:ethyl acetate) as a white solid, mp >260° C., identified by IR,¹ HNMR, ¹⁹ FNMR and mass spectral analyses.

EXAMPLE 18

Preparation of 5-Nitro-2-(trifluoromethyl)indole ##STR35##

A solution of 2-(trifluoromethyl)indole (0.2 g, 1.1 mmole) in aceticanhydride is treated with (0.131 g, 0.54 mmole of) Cu(NO₃)₂.3H₂ O at 0°C., stirred for 2.5 hours at room temperature and diluted with water andether. The phases are separated; the organic phase is washedsequentially with saturated NaHCO₃ and brine, dried over MgSO₄ andconcentrated in vacuo to give a yellow solid residue. The residue ischromatographed (silica gel/20% ethyl acetate in hexanes) to give thetitle product as a yellow solid, 0.073 g (29.4% yield), mp 190°-193° C.,identified by IR, ¹ HNMR, ¹⁹ FNMR and mass spectral analyses.

EXAMPLE 19

Preparation of 5-Nitro-2-(trifluoromethyl)indole and3-cyano-6-nitro-2-(trifluoromethyl)indole-3-carbonitrile ##STR36##

Using essentially the same procedure described in Example 18 andsubstituting 3-cyano-2-(trifluoromethyl)indole as substrate the titleproduct mixture is obtained. The mixture is separatedchromatographically (silica gel/20% ethyl acetate in hexanes) andrecrystallized from ethyl acetate/hexanes to give:

A--3-cyano-5-nitro-2-(trifluoromethyl)indole as beige crystals in 41%yield, mp>260° C. identified by IR, ¹ HNMR, ¹⁹ FNMR and mass spectralanalyses, and

B--3-cyano-6-nitro-2-(trifluoromethyl)indole as a beige solid in 6%yield, mp>230° C., identified by IR, ¹ HNMR, ¹⁹ FNMR and mass spectralanalyses.

EXAMPLE 20

Preparation of 3,5-Dinitro-2-(trifluoromethyl)indole ##STR37##

Using essentially the same procedure described in Example 18 andsubstituting 5-nitro-2-(trifluoromethyl)indole as substrate the titleproduct is obtained in 16.7% yield (90% pure) as a yellow solid, mp225°-228° C., identified by IR, ¹ HNMR, ¹⁹ FNMR and mass spectralanalyses.

EXAMPLE 21

Preparation of 5,6- and5,7-Dinitro-2-(trifluoromethyl)indole-3-carbonitrile ##STR38##

A mixture of 3-cyano-5-nitro-2-(trifluoromethyl)indole (0.23 g, 0.90mmole) in 7 mL of fuming nitric acid (90%), under nitrogen, is stirredat 0° C. for 0.5 hour, stirred for 19 hours at room temperature, pouredinto ice water and extracted with ethyl acetate. The combined extractsare washed sequentially with saturated NaHCO₃ and brine, dried overMgSO₄ and concentrated in vacuo to give a brown solid residue. Afterchromatography and crystallization, the title product mixture isobtained as a yellow solid, 0.104 g (3.7% yield), mp >230° C.,identified by IR, ¹ HNMR and ¹⁹ FNMR analyses.

EXAMPLE 22

Preparation of 5-Methoxy-2-(trifluoromethyl)indole ##STR39##

Tetramethylethylenediamine (TMEDA) (49 g, 0.42 mole), under nitrogen, istreated with n-butyl lithium (168 mL of 2.57N in hexanes, 0.42 mole) at0° C., stirred for 0.5 hour at room temperature, treated dropwise withN-(trimethylsilyl)-4-methoxy-o-toluidine (40.0 g, 0.19 mole) , heated atreflux temperature for 4 hours, cooled to -78° C., diluted with drycyclohexane, treated dropwise with ethyl trifluoroacetate (45 g, 0.23mole), stirred at -78° C. for 0.5 hour, warmed to room temperature andquenched with saturated NH₄ Cl solution. The mixture is extracted withdiethyl ether. The combined extracts are washed sequentially withsaturated NH₄ Cl and brine, dried over Na₂ SO₄ and concentrated in vacuoto give a brown oil residue. The oil is chromatographed (silica gel/10%ethyl acetate in hexanes) to give the title product as white needles,5.0 g (12% yield), mp 60° C. (after recrystallization from pentane),identified by IR, ¹ HNMR, ¹³ CNMR, ¹⁹ FNMR and mass spectral analyses.

EXAMPLE 23

Preparation of 3-cyano-5-methoxy-2-(trifluoromethyl)indole ##STR40##

A solution of 5-methoxy-2-(trifluoromethyl)indole (3.0 g, 13.0 mmole) inacetonitrile is treated dropwise with chlorosulfonyl isocyanate (2.02 g,14.3 mmole) at 0° C., stirred at ambient temperatures for 2.5 hours,treated with dimethylformamide (DMF) (2.1 g, 28.6 mmole), stirred atambient temperatures for 0.75 hour and poured into water. The resultantmixture is extracted with diethyl ether. The combined extracts arewashed sequentially with water and brine, dried over MgSO₄ andconcentrate in vacuo to give a brown oil residue. The oil iscrystallized in ether/hexanes to give the title product as browncrystals, 0.78 g (25% yield), mp 189°-190° C., identified by IR, ¹ HNMR,¹³ CNMR and ¹⁹ FNMR.

EXAMPLE 24

Preparation of 5,6-Dichloro-2-(2-chloro-1,1,2-trifluoroethyl)thio!indole ##STR41##

A mixture of 5,6-dichloroindolene-2-thione (3.71 g, 17.0 mmole) andpotassium carbonate (2.35 g, 17.0 mmole) in isopropanol is placed in apressure tube, treated with chlorotrifluoroethylene (2.18 g, 18.7mmole), sealed and stirred for 16 hours at room temperature. After theseal is broken, the reaction mixture is concentrated in vacuo, dilutedwith ethyl acetate, washed sequentially with water and brine, dried overMgSO₄ and reconcentrated in vacuo to afford a dark residue. Flash columnchromatography (silica gel/l:10 ethyl acetate: hexanes) gives the titleproduct as an off-white solid, 3.4 g (56% yield) mp 54°-60° C.,identified by IR, ¹ HNMR and ¹⁹ FNMR analyses.

EXAMPLES 25-27

Preparation of Substituted 2-thioindole compounds ##STR42##

Using essentially the same procedure described in Example 24 andsubstituting the appropriate indoline-2-thione substrate and desiredolefin, the following compounds shown in Table I are obtained. T1 TABLEI-? - ##STR43##

EXAMPLE 28

Preparation of 2-(2-chloro-1,1,2-trifluoroethyl)thio!indole-3-carbonitrile ##STR44##

A solution of 2- (2-chloro-1,1,2-trifluoroethyl)thio!indole (0.64 g, 2.4mmole) in acetonitrile is treated with a solution ofchlorosulfonylisocyanate (CSI) (0.85 g, 6.0 mmole) in acetonitrile atice bath temperatures, stirred at room temperature for 3 hours, treatedwith dimethylformamide (0.88 g, 12 mmole) at 0° C., stirred for 1 hourat ambient temperatures, poured into ice water and extracted with ethylacetate. The combined extracts are washed with brine, dried over MgSO₄and concentrated in vacuo to give a residue. Flash chromatography(silica gel/1:4 ethyl acetate:hexanes) affords the title product as awhite solid, 0.44 g (63% yield), mp 134°-136° C., identified by IR, ¹HNMR and ¹³ CNMR.

EXAMPLE 29

Preparation of 5-Bromo-2(2-chloro-1,1,2-trifluoroethyl)thio!indole-3-carbonitrile ##STR45##

Using essentially the same procedure described in Example 28 butemploying 5-bromo-2 (2-chloro-1,1,2-trifluoroethyl)thio!indole, thetitle product is obtained as a white solid, mp 187°-192° C., identifiedby IR, ¹ HNMR and ¹³ CNMR.

EXAMPLE 30

preparation of 2-(trifluoromethyl)-3- (trifluoromethyl)thio!indole##STR46##

A mixture of 2-(trifluoromethyl)indole (1.85 g, 0.01 mole) and 3 dropsof triflic acid in dichloroethane is heated at 65° C. in a sealedpressure tube for 72 hours, cooled, concentrated in vacuo, diluted withethyl acetate, washed sequentially with saturated NaHCO₃ and brine,dried over NaSO₄ and reconcentrated in vacuo to give a residue. Flashcolumn chromatography (silica gel/1:10 ethyl acetate:hexanes) affordsthe title product as a yellow oil, 2.03 g (71% yield), identified by IR,¹ HNMR, ¹³ CNMR, ¹⁹ FNMR and mass spectral analyses.

EXAMPLE 31

Preparation of 2,6-Dibromo-3- (trifluoromethyl)thio!indole ##STR47##

A mixture of 3- (trifluoromethyl)thio!indole (0.776 g, 3.57 mmole), 1.0g of silica gel and N-bromosuccinimide (NBS) (1.27 g, 71.9 mmole) inmethylene chloride is stirred at room temperature for 2 hours andconcentrated in vacuo to give a residue. Flash column chromatography(silica gel/15:85 ethyl acetate:hexanes) of the residue affords thetitle product as a brown syrup, 0.41 g (30.6% yield), identified by IR,¹ HNMR, ¹³ CNMR, ¹⁹ FNMR and mass spectral analyses.

EXAMPLE 32

Preparation of 5-Bromo-2(2-chloro-1,1,2-trifluoroethyl)thio!indole-3-carbonitrile ##STR48##

A solution of 2 (2-chloro-1,1,2-trifluoroethyl)thio!indole (0.75 g, 2.58mmole) in acetic acid is treated with bromine (0.45 g, 2.84 mmole),stirred for 16 hours at room temperature, poured into water andfiltered. The white solid filtercake is dissolved in ethyl acetate,washed with brine, dried over MgSO₄ and concentrated in vacuo to give aresidue. The residue is chromatographed (silica gel/1:4 ethylacetate:hexanes) to afford the title product as a white solid, 0.28 g(29% yield), mp 187°-192° C., identified by IR, ¹ HNMR, ¹³ CNMR, ¹⁹ FNMRand mass spectral analyses.

EXAMPLES 33-36

Preparation of Bromo- and Dibromo-substituted -3-(trifluoromethyl)indole compounds ##STR49##

Using essentially the same procedure described in Example 32,substituting the appropriately substituted indole substrate andemploying one or two equivalents of Br₂, the following compounds shownin Table III are obtained.

                  TABLE III    ______________________________________     ##STR50##    Example                        mp    Number      R.sub.m     Z      °C.    ______________________________________    33          5-Br        CF.sub.3                                   76-78    34          5,6-diBr    CF.sub.3                                   syrup    35          5-Br        CN     172-175    36          6-Br        CN     153-156    ______________________________________

EXAMPLE 37

Preparation of 2-(Trifluoromethyl)-3- (trifluoromethyl)sulfinyl!indole##STR51##

A mixture of 2-(trifluoromethyl)-3- (trifluoromethyl)thio!indole (0.96g, 3.36 mmole) and 30% hydrogen peroxide (1.15 mL, 10.1 mmole) in aceticacid is heated at 50° C. for 16 hours, cooled to room temperature,poured onto water and filtered. The filter cake is air-dried to give thetitle product as a colorless solid, 0.535 g (50% yield), mp 183°-185°C., identified by IR, ¹ HNMR, ¹³ CNMR, ¹⁹ FNMR and mass spectralanalyses.

EXAMPLES 38-41

Preparation of Substituted-3- (haloalkyl)sulfinyl!indole compounds##STR52##

Using essentially the same procedure described in Example 37 andemploying the appropriate 3- (trifluoromethyl)thio!indole substrate, thecompounds shown in Table IV are obtained.

                  TABLE IV    ______________________________________     ##STR53##    Example                     mp    Number    R.sub.m  Z        °C.    ______________________________________    38        5-Br     CF.sub.3 210-212    39        H        CN       154-156    40        H        CONH.sub.2                                185 (decompose)    41        6-Br     Br       95-97    ______________________________________

EXAMPLE 42

Preparation of 2(2-Chloro-1,1,2-trifluoroethyl)sulfonyl!indole-3-carbonitrile ##STR54##

A mixture of 2 (2-chloro-1,1,2-trifluoroethyl)thio!indole-3-carbonitrile(2.39 g 8.22 mmole) and 30% hydrogen peroxide (2.80 g, 24.7 mmole) inacetic acid is heated at 60° C. for 16 hours, cooled to room temperaturepoured onto water and filtered. The filtercake is air-dried to affordthe title product as a white solid, 2.37 g (89% yield), mp 164°-167° C.,identified by IR, ¹ HNMR, ¹³ CNMR and ¹⁹ FNMR analyses.

EXAMPLES 43-48

Preparation of Substituted-sulfonylindole compounds ##STR55##

Using essentially the same procedure described in Example 42, employingthe appropriate thioindole substrate and heating to about 60°-90° C.,the compounds shown in Table V are obtained.

                  TABLE V    ______________________________________     ##STR56##    Example                              mp    Number  R.sub.m  Z            Y      °C.    ______________________________________    43      5,6-diCl SO.sub.2 CF.sub.2 CHFCl                                  CN     178-180    44      5-Br     SO.sub.2 CF.sub.2 CHFCl                                  CN     220-223    45      H        H            SO.sub.2 CF.sub.3                                         115-118    46      H        CF.sub.3     SO.sub.2 CF.sub.3                                         104-107    47      H        CN           SO.sub.2 CF.sub.3                                         152-154    48      5-Br     CN           SO.sub.2 CF.sub.3                                         >230    ______________________________________

EXAMPLE 49

Preparation of 3-Bromo-5,6-dichloro-2(2-chloro-1,1,2-trifluoroethyl)sulfonyl!indole ##STR57##

A mixture of 5,6-dichloro-2(2-chloro-1,1,2-trifluoroethyl)sulfonyl!indole (0.84 g, 2.29 mmole) andsodium acetate (0.21 g, 2.52 mmole in acetic acid is treated withbromine (0.40 g, 2.52 mmole), stirred for 0.5 hour at room temperature,poured onto water and filtered. The filtercake is air-dried to affordthe title product as a white solid, 0.93 g (91% yield), mp 200°-205° C.,identified by IR, ¹ HNMR and ¹⁹ FNMR spectral analyses.

EXAMPLE 50

Preparation of 2-(2-chloro-1,1,2-trifluoroethyl)sulfonyl!-1-(ethoxymethyl)indole-3-carbonitrile##STR58##

A mixture of 2(2-chloro-1,1,2-trifluoroethyl)sulfonyl!indole-3-carbonitrile (1.0 g,3.1 mmole), chloromethylethylether (0.35 g, 3.72 mmole), and 95%potassium t-butoxide (0.44 g, 3.72 mmole) in tetrahydrofuran is stirredat room temperature for 16 hours, treated with 1.55 mmole additionalchloromethylethylether and potassium t-butoxide, stirred at roomtemperature for another 16 hours, concentrated in vacuo, diluted withethyl acetate, washed sequentially with water and brine, dried overMgSO₄ and reconcentrated in vacuo to give an oil residue. After flashcolumn chromatography (silica gel/1:4 ethyl acetate: hexanes) the titleproduct is obtained as a white solid, 0.32 g (28% yield), mp 97°-100°C., identified by IR and ¹ HNMR analyses.

EXAMPLES 51-61

Preparation of Substituted-1-(ethoxymethyl)indole compounds ##STR59##

Using essentially the same procedure described in Example 50 andemploying the appropriately substituted indole, the compounds in TableVI are obtained.

                  TABLE VI    ______________________________________     ##STR60##    Example                              mp    Number  R.sub.m Z            Y       °C.    ______________________________________    51      5-Br    SO.sub.2 CF.sub.2 CHFCl                                 CN      146-147    52      H       CF.sub.3     SOCF.sub.3                                          99-102    53      H       H            SO.sub.2 CF.sub.3                                         97-98    54      H       CF.sub.3     SCF.sub.3                                         58-60    55      H       H            SCF.sub.3                                         60-62    56      5-Br    CF.sub.3     SCF.sub.3                                         oil    57      H       CN           H       50-52    58      H       CN           SOCF.sub.3                                         101-103    59      H       CN           SO.sub.2 CF.sub.3                                         124-126    60      H       CF.sub.3     SO.sub.2 CF.sub.3                                         93-94    61      6-Br    Br           SCF.sub.3                                         oil    ______________________________________

EXAMPLE 62

Preparation of 3', 5'-Dichloroacetophenone,(3,5-dichlorophenyl)hydrazone ##STR61##

A mixture of 2,4-dichlorophenylhydrazine (4.25 g, 0.025 mole),3,5-dichloroacetophenone (4.5 g, 0.024 mole) and 1.0 mL HCl in ethanolis heated at reflux temperature for 1 hour, cooled and filtered. Thefiltercake is air-dried to afford the title product as a white solid,6.2 g (74% yield), mp 110°-111° C., identified by IR and ¹ HNMRanalyses.

EXAMPLE 63

Preparation of 5,7-Dichloro-2-(3,5-dichlorophenyl)indole ##STR62##

A mixture of 3', 5'-dichloroacetophenone, (3,5-dichlorophenyl)hydrazone(5.2 g, 0.015 mole) and 20 mL of polyphosphoric acid (PPA) is heated at175°-180° C. for 2 hours, cooled, treated with ice and allowed to standat room temperature. The resultant mixture is extracted with diethylether. The combined extracts are dried over anhydrous K₂ CO₃ andconcentrated in vacuo to afford the title product as a brown solid, 4.35g (87.8% yield), mp 189°-190° C., identified by IR and ¹ HNMR analyses.

EXAMPLE 64

Preparation of5,7-Dichloro-2-(3,5-dichlorophenyl)-3-(trifluoromethylcarbonyl)indole##STR63##

A solution of 5,7-dichloro-2-(3,5-dichlorophenyl)indole (2.0 g, 6.0mmole) in dimethylformamide is treated with 1.0 mL of trifluoroaceticanhydride at 0°-5° C., stirred for 1 hour, heated at 50°-60° C. for 1hour, stirred at ambient temperatures for 72 hours, poured over ice andextracted with diethyl ether. The combined extracts are washedsequentially with water and brine, dried over anhydrous K₂ CO₃ andconcentrated in vacuo to afford the title product as an off-white solid,1.6 g (62% yield), mp 214°-216° C., identified by IR and ¹ HNMRanalyses.

EXAMPLE 65

Preparation of 5,7-Dichloro-2-(3,5-dichlorophenyl)-3-nitroindole##STR64##

A mixture of 5,7-dichloro-2-(3,5-dichlorophenyl)indole (1.25 g, 3.8mmole) in acetic acid is treated dropwise with 3 mL of concentrated HNO₃at 90° C., maintained at 90° C. for 1 hour, cooled and filtered. Thefiltercake is air-dried and recrystallized from methanol/water to affordthe title product as a yellow solid, 0.60 g, (42% yield), mp 272°-273°C., identified by IR, ¹ HNMR and elemental analyses.

EXAMPLE 66

Preparation of 5,7-dichloro-2-(3,5-dichlorophenyl)-3-(trifluoromethyl)sulfonyl!indole ##STR65##

A solution of 5,7-dichloro-2-(3,5-dichlorophenyl)indole (2.0 g, 6.0mmole) in dimethylformamide is treated with 1 mL oftrifluoromethylsulfonyl anhydride at 0°-5° C., stirred at ambienttemperatures for 0.5 hour, heated at 50°-60° C. for 1 hour, stirred for72 hours at room temperature, poured over ice and filtered. Thefiltercake is air-dried to afford the title product as an off-whitesolid, 1.65 g (59% yield), mp 300°-302° C., (decompose), identified byIR and ¹ HNMR and elemental analyses.

EXAMPLE 67

Preparation of 3,5,7-trichloro-2-(p-chlorophenyl)indole ##STR66##

A solution of 5,7-dichloro-2-(p-chlorophenyl)indole in tetrahydrofuranis treated dropwise with 1.0 mL of thionyl chloride, stirred for 16hours at room temperature, poured over ice and filtered. The filtercakeis air-dried to afford the title product as a yellow solid, 0.85 g (76%yield), mp 148°-149° C., identified by IR, ¹ HNMR and elementalanalyses.

EXAMPLES 68-85

Preparation of 2-(Substituted phenyl)indole compounds ##STR67##

Using essentially the same procedures described in Examples 62 through67 and employing the appropriate reagents, the compounds shown in TableVII are obtained.

                  TABLE VII    ______________________________________     ##STR68##    Example                                   mp    Number R.sub.m  Y        L     M    Q     °C.    ______________________________________    68     4,6-diCl H        3-Cl  H    5-Cl  210-212    69     4,7-diCl H        3-Cl  H    5-Cl  202-203    70     5,7-diCl H        H     4-Cl H     165-166    71     4,7-diCl NO.sub.2 3-Cl  H    5-Cl  115-117    72     4,6-diCl NO.sub.2 3-Cl  H    5-Cl  258-260    73     4,6-diCl NO.sub.2 H     4-Cl H     248-250    74     5,7-diCl NO.sub.2 H     4-Cl H     290-291    75     4,7-diCl COCF.sub.3                             3-Cl  H    5-Cl  198-199    76     4,6-diCl COCF.sub.3                             3-Cl  H    5-Cl  165-166    77     5,7-diCl COCF.sub.3                             H     4-Cl H     112-113    78     4,7-diCl SO.sub.2 CF.sub.3                             3-Cl  H    5-Cl  212-213    79     4,6-diCl SO.sub.2 CF.sub.3                             3-Cl  H    5-Cl  304-306    80     4,7-diCl Br       3-Cl  H    5-Cl  --    ______________________________________

EXAMPLE 81

Insecticidal And Acaricidal Evaluation Of Test Compounds

Test solutions are prepared by dissolving the test compound in a 35%acetone in water mixture to give a concentration of 10,000 ppm.Subsequent dilutions are made with water as needed.

Spodoptera eridania, 3rd instar larvae, southern armyworm (SAW)

A Sieva limabean leaf expanded to 7-8 cm in length is dipped in the testsolution wtih agitation for 3 seconds and allowed to dry in a hood. Theleaf is then placed in a 100×10 mm petri dish containing a dampfilterpaper on the bottom and ten 3rd instar caterpillars. At 5 days,observations are made of mortality, reduced feeding, or any interferencewith normal molting.

Diabrotic undecimpunctata howardi, 3rd instar southern corn rootworm(SCR)

One cc of fine talc is placed in a 30 mL wide-mount screw-top glass jar.One mL of the appropriate acetone suspension is pipetted onto the talcso as to provide 1.25 and 0.25 mg of active ingredient per jar. The jarsare set under a gentle air flow until the acetone is evaporated. Thedried talc is loosened, 1 cc of millet seed is added to serve as foodfor the insects and 25 mL of moist soil is added to each jar. The jar iscapped and the contents thoroughly mixed on a Vortex Mixer. Followingthis, ten 3rd instar rootworms are added to each jar and the jars areloosely capped to allow air exchange for the larvae. The treatments areheld for 6 days before mortality counts are made. Missing larvae arepresumed dead, since they decompose rapidly and cannot be found. Theconcentrations of active ingredient used in this test correspondapproximately to 50 and 10 kg/ha, respectively.

Tetranychus urticae(OP-resistant strain), 2-spotted spider mite (TSM)

Sieva limabean plants with primary leaves expanded to 7-8 cm areselected and cut back to one plant per pot. A small piece is cut from aninfested leaf taken from the main colony and placed on each leaf of thetest plants. This is done about 2 hours before treatment to allow themites to move over to the test plant to lay eggs. The size of the cut,infested leaf is varied to obtain about 100 mites per leaf. At the timeof test treatment, the piece of leaf used to transfer the mites isremoved and discarded. The newly mite-infested plants are dipped in thetest solution for 3 seconds with agitiation and set in the hood to dry.After 2 days, one leaf is removed and mortality counts are made. After 5days, another leaf is removed and observations are made of mortality ofthe eggs and/or newly emerged nymphs.

Empoasca abrupta, adults, western potato leafhopper (LH)

A Sieva limabean leaf about 5 cm long is dipped in the test solution for3 seconds with agitation and placed in a hood to dry. The leaf is placedin a 100×10 mm petri dish containing a moist filter paper on the bottom.About 10 adult leafhoppers are added to each dish and the treatments arekept for 3 days before mortality counts are made.

Heliothis virenscens, 3rd instar tobacco budworm (TBW)

Cotton cotyledons are dipped in the test solution and allowed to dry ina hood. When dry, each is cut into quarters and ten sections are placedindividually in 30 mL plastic medicine cups containing a 5 to 7 mm longpiece of damp dental wick. One 3rd instar caterpillar is added to eachcup and a cardboard lid placed on the cup. Treatments are maintained for3 days before mortality counts and estimates of reduction in feedingdamage are made.

Diabrotica virgifera virgifera Leconte, 3rd instar western corn rootworm(WCR)

One cc of fine talc is placed in a 30 mL wide-mouth screw-top glass jar.One mL of the appropriate acetone test solution is pipetted onto thetalc so as to provide 1.25 mg of active ingredient per jar. The jars areset under a gentle air flow until the acetone is evaporated. The driedtalc is loosened, 1 cc of millet seed is added to serve as food for theinsects and 25 mL of moist soil is added to each jar. The jar is cappedand the contents thoroughly mixed mechanically. Following this, ten 3rdinstar rootworms are added to each jar and the jars are loosely cappedto allow air exchange for the larvae. The treatments are held for 5 dayswhen mortality counts are made. Missing larvae are presumed dead, sincethey decompose rapidly and can not be found. The concentrations ofactive ingredient used in this test correspond approximately to 50kg/ha.

The tests are rated according to the scale shown below and the dataobtained are shown in Tables VIII and IX. When more than one test isconducted, the results are averaged.

    ______________________________________    RATING SCALE           Rate % Mortality    ______________________________________           0    no effect           1    10-25           2    26-35           3    36-45           4    46-55           5    56-65           6    66-75           7    76-85           8    86-99           9    100           --   not tested    ______________________________________

                  TABLE VIII    ______________________________________    Insecticidal And Acaricidal Evaluation Of Substituted    Indole Compounds    % Mortality    SAW            SCR              LH    Compound            (1000  (300    (50  TSM     (300 TBW    (Ex. No.)            ppm)   ppm)    ppm) (300 ppm)                                        ppm) (100 ppm)    ______________________________________     2      0      --      0    8       0    0     4      0      --      9    0       --   --     5      9      --      0    0       --   9     9      0      --      0    0       --   --    10      9      --      9    0       --   --    11      --     9       --   9       --   9    12      --     --      --   0       --   --    13      --     9       0    8       7    9      14A   --     9       7    8       9    9      14B   --     9       9    6       9    9      15A   --     3       4    8       1    0      15B   8      9       9    0       2    1    16      --     9       9    8       9    --    17      --     9       9    8       9    9    18      --     2       0    0       0    0      19A   --     9       0    0       3    5      19B   --     0       0    0       0    0    20      --     7       0    0       0    0    21      --     8       9    5       3    3    22      --     0       0    3       0    1    23      --     0       0    3       0    1    ______________________________________

                  TABLE IX    ______________________________________    Insecticidal And Acaricidal Evaluation Of Substituted    Indole Compounds    % Mortality    SAW           WCR               LH    Compound            (1000  (300    (50  TSM     (100 TBW    (Ex. No.)            ppm)   ppm)    ppm) (300 ppm)                                        ppm) (100 ppm)    ______________________________________    24      9      --     2     8       --   --    25      0      --     3     7       --   --    26      0      --     2     5       --   --    27      7      --     0     9       --   --    28      2      --     0     0       --   --    29      9      9      0     0       --   --    30      0      --     0     0       --   --    31      9      4      0     4       0    0    33      9      9      5     4       9    0    34      9      --     9     9       --   --    35      9      --     0     8       --   --    37      9      9      0     0       --   --    38      8      9      0     0       --   --    39      9      --     2     3       --   --    40      0      --     3     0       --   --    41      9      --     2     0       --   --    42      9      --     6     0       8    4    44      9      --     0     9       --   --    45      0      --     0     0       --   --    46      9      9      9     4       9    8    47      9      --     0     9       --   --    50      8      3      3     4       --   --    51      2      --     0     9       --   --    52      9      9      6     7       8    0    53      0      --     4     0       --   --    54      0      --     7     0       --   --    55      0      --     9     0       --   --    56      9      9      8     7       9    0    57      4      --     2     0       --   --    58      9      --     9     3       --   --    59      9      --     8     0       --   --    60      9      --     9     5       --   --    62      2      --     0     0       --   --    63      5      --     0     0       --   --    64      9      --     8     8       --   --    65      9      --     9     0       --   --    66      0      --     0     0       --   --    68      7      --     2     0       --   --    69      7      --     0     0       --   --    71      9      --     7     0       --   --    75      9      --     0     0       --   --    78      0      --     0     0       --   --    ______________________________________

What is claimed is:
 1. A method for the control of insect or acaridpests which comprises contacting said pests of their food supply,habitat or breeding grounds with a pesticidally effective amount of acompound formula I ##STR69## wherein Y and Z are each independently CNor C₁ haloalkyl; R is halogen, m is 2 and A is hydrogen.
 2. The methodof claim 1 wherein C₁ haloalkyl is trifluoromethyl and R is chlorine. 3.A method for the protection of growing plants from attack or infestationby insect or acarid pests which comprises applying to the foliage of theplants, or to the soil or water in which they are growing, apesticidally effective amount of a compound of formula I ##STR70##wherein Y, Z, A, R and m are as described in claim
 1. 4. The method ofclaim 3 wherein C₁ haloalkyl is trifluoromethyl and R is chlorine.